Diels-Alder Reaction of 6,6-Dimethylfulvene with 2-Acetoxyacrylonitrile. Preparation of 5-(2-Hydroxyethyl)-2-cyclopenten-1-one

Article abstract of DOI:10.1021/jo00171a043

The Diels-Alder reaction of 6,6-dimethylfulvene with 2-acetoxyacrylonitrile gave two different adducts, 2-acetoxy-2-cyano-7,7-isopropylidenebicyclo<2.2.1>hept-5-ene (3, 70percent) and 2-acetoxy-2-cyano-1-isopropenylbicyclo<2.2.1>hept-5-ene (4, 18percent).The formation of 4, which has not been reported before, can be suppressed by adding pyridine to the reaction mixture.Hydrolysis of 3 by sodium methoxide, followed by successive treatment with unsolvated hydroxide ion, peroxyformic acid, lithium aluminum hydride, and lead tetraacetate, gave 5-(2-hydroxyethyl)-2-cyclopenten-1-one (15, 35percent from 3).